Metallizable azo dyes containing a pyrazolone radical



Patented Jan. 27, 1 943 METALLIZABLE AZO ores CONTAINING A r-YRAzoLoRADICAL Robert SidneyLong and Charles Edward 'LeWiS, iSoinerville,N.'J.,assignors to American Cyanamid Company, New York, Y., a corporation 91'Ma n NoD awing.

1 This invention relates to 'az'o ,dyestuiis capable of beingmeta'llized derived "from 3-a mino-l 5;- pyrazolonesas couplingcomponents. The dyestuffs may be represented by the following formula:

Throughout the specification an'dclaims the term acyl" will be used inits more limited sense to define the radical of a carboxylic acid. Theterm will have no other'ine'an'ingj The produotsof the-presentinvent-ion arepre pared in general by coupling onto the auras solubleenols of the pyraz'ol'on'e with diazotiz'edaromatic amines whichcontain-lake forming groups in the ortho-po'sition to'the diazo grou It''i's also convenient to prepare the dyestufis' contain} ing acylaminogroups in' the ii-position "ofthe pyrazolone nucleus'by 'reactingfirstthe aminopyrazolone with-an excess of acylating agent using theresulting 'pyrazolederivative' as'the coupling component, since theacylfgroup attached to the oxygen atom split'ofi bytheaction of alkalineagent'sjat' ordinary'tempe'raturs.

The resulting dyestuffs are valua le per se for dyeing animal fibres;They are also useful in processes such 'as the metachr'om'e process inwhich metallizing takes place in the dye bath, or in processes involvingseparate treatment with metal on the goods, such asfor example, top orbottom chroming processes.

Since the products of the present invention contain lake forming groupsortho to the azo group in both components, they are capable of formingstable metal complexes with the ,common metallizing agents.

Some typical pyrazolones of the above type which are useful in preparingthe products of Application December 8,1944, ,serial No. 567,306

s cla (01. 260-162) the present invention :are i those in which X and Yare both hydrogen and R is asdefined-for example, 1-phenyl-3-amino-5pyrazolone,l- (alphanaphthyl) -3-amino 5 -pyrazolone, l-(4'-methoyphenyl)-3-amin0- z 1c n ylphenyl) 3-amino 5 pyrazolone, 1-( l"- ch-lorophenyl) -3- amino-5-pyra zolone, l-tflf-suliophenyl)-3-amino-5-pyra-zolone, l- (3 -nitrophenyll -3- amino 5 pyrazolone, -3;-amino 5 pyrazolone; those in which X is hydrogen, Y is an acyl radiical, and R is as defined, for example, 1-p h e1 1yl -Zf, a v i 5 p a l n-phe :3-. snz.o l: amino5-pyrazo lone; those in which 2; is H, Y is an ay radical, n R i a d fine q s amr l h W N-phwflm -5-mazel ne- Thepreferred products of the'present inven tion are the azo dyestuffsderived from th razolines in whichR is an aromatic radicals of thebenzene series,these being readily obtained through o d on o mqn rw siuie 1 drazines with esters of cyanoacetic acid in the presence ofalkaline condensing agents (see Weissberger and Porter; J. Am. vC heirn. ,SQc. 5 2133 (1942).

The diazo components useful in preparingthe products of thepresentinvention arethose that have in the ortho position to the diazo'group agroup that can be converted into a nr etal com plex such as,particularly, the hydroxy group, the carboxylic acid group, and also thealkoxy group and halogen which, under specific condi tions in theprocess oflmetallization', may bereplac'ed by the complex-forminghydro'xyl. {Some typical examples of useful Idiazo' ieomee e t are2-amino-4-nitrophenol, 2-amin'o 5-nitrop'henol, 2-amino-4-ohlorophenol,3-amino-4-hydroxybenzenesulfonic acid, 2 1fnethyl4amino-5;hydroxybenzenesulfonic acid, 2 nitrofl-amin0 5 5,hydroxybenzenesulfonic acid, 2-ohloro 4amino-.5 hydroxyben'zenesulfonicacid, 2-hydroXy-3-amino- 5-chlorbenzenesulfonic acid,3-,amino-l-hydroxy-5-nitrobenzenesulfonic acid, 2 113 61016 3- am'in0-5nitrobenzenesulfonic acid, 2 -hydroxjyj-3- amino-5-suliobenzo'ic acid,'2-aminoe5-sul'foben- 'zoic acid, anthranilic'acid, I-aminQQ-hydroiiynaphthalenel-sulfonic acid, Lamino-Q-hydroky- 6-nitronaphthalenel-su1ionic acid, v3,3'-dic hlorobenzidine,o-dianisidine, 1-(4- sulfophenyl)- 3-methyl-fl-amino-5Dyrazolone, andthe like.

The diazo component may be also further substitutedby azogroups and theaminopyrazolones may be used also as end components in polyazo in thismanner is slightly bluer than the shade dyes. obtained in Example 2using the top chrome pro- The invention i illustrated by the followingcedure. examples, the parts being by weight. Example 4 To a cooledsolution of 1.8 parts of 1-phenyl-3- anilinopyrazolonein 30 parts ofwater and 2 parts of 20% sodium hydroxide is added a solution of 2 partsof the diazo compound from 1- A solution of 1.8 parts of1-pheny1-3-aminopyrazolone-5 in parts of water and 3 parts of 20% sodiumhydroxide is cooled to about 10 C. and to it is added slowly a solutionof 2.8 parts aminO 2 hydmXy 4 naphthalenesulfomc acid of the diazocompound of 1-amino-2-hydr0xy- (purity 89%) in 10 parts of water and 2parts of 4'naphtha'1ene sulfomc acld (punty 892%) m 20 Q 20% sodiumhydroxide. A deep red solution is parts of water and 2 parts of 20%sodium hyobtained and after stirring for a short time the F reactmnmniwre 1S i m coupling reaction is complete. Acidifying the recouplmg 15complete and is t dlluted wlth action mixture with mineral acid producesa dark about an equal quantity of Water- T azo dye 15 red, gelatinousproduct which is coagulated by obtained as a bright red solid byacidification with diluting and heating The dark red solid so mmeml acldand filtratlontained is then removed by filtration and dried at Example2 ith th' e t 1' a 1 d en 18 pro no is app 1e on woo as an aci sogltmn iparttof i dyestufi by the procedure described in Example 2,

Z E i f i 0 o there is obtained a level reddish-yellow shade 5 5a andpar 5 50 p or which is converted to a blue tone bordeaux by the ammomumsulfate m 300 parts Water 13 top chrome procedure described also inExample pared 5 Parts of wool flannel place goods t 2. The self-shadedyeing is also converted to a scoured, rinsed, and added, and the wholeis boiled for one-half hour, water being added as ggj ii d g g gzprocedure deneeded to maintain constant volume. There are then added 1.5parts of a 10% solution of acetic Example 5 acid and boiling iscontinued for one-half hour. N In this manner the dyestuff dyes wool anatl tractive rust shade of good fastness to light and 40 washing.

5 parts of previously scoured wool flannel are dyed in a similar mannerand after boiling in the dye bath for one-half hour there are added 1Q0311 1.5 parts of a 10% solution of acetic acid and boiling iscontinued for one-half hour. The dyeing is top-chromed by adding 4 partsof a 1% To a cooled solution prepared from 2.6 parts solution ofpotassium dichromate and boiling for of l-phenyl-3-acetylamino 5acetoxypyrazole, 40 minutes. The rust self-shade is thus con- 20 partsof water, and 4 parts-of 20% sodium hyverted to an attractive bordeauxtint of improved 5 droxide is added a solution of 2.8 parts of thefastness properties. diazo compound from 1-amino-2-hydroxy-4- The dyeingmay also be after-treated with naphthalene-sulfonic acid (purity 89.2%)in 20 other metals by boiling in a bath containing a parts of water and2 parts of 20% sodium bysalt of the metal and a slight excess of aceticdroxide. The coupling reaction is complete after acid. In this mannerthe acid dyeing obtained stirring for a short time at room temperatureand above is converted to attractive bluish-red, redthe dyestufi isisolated as the sodium salt by the dish-orange, and orange shades withsalts of addition of sodium chloride. The product is recopper. t, and irespe tively. moved by filtration.

Example 3 7 When the azo dyestuff is applied as an acid color on wool bythe procedure of Example 2, In Order to apply the M0 dyestufi of EXample1 there is obtained an attractive reddish-yellow t0 W001 by themetachrome F there is P shade which is converted to a bordeaux by thepared a Solution of the followmg Ciomloosmon: topchrome procedure. Asimilar bordeaux shade parts is obtained by the metachrome procedure.The azo dye from Example 1 0.05 Example 6 A 10% solution of Glauberssalt 5.00 A 10% solution of ammonium sulfate 4.00 N N CHCNHCOCH3 A 1%solution of potassium dichromate--- 4.00 Water 300.00 G00H N To thesolution is then added the wool mate- N rial to be dyed and the whole isboiled for 40 minutes. There are then added 1.5 parts of a 308K 10%solution of acetic acid and boiling is continued for one-half hour. Theshade obtained wearers The diazo compound from 2-amino-5-sulfobenzoicacid is prepared in the usual manner from 2.8 parts of2-amino-5-sulfoben'z'oic acid (purity 78.3%), 15 parts of Water, '7parts of 17% hydrochloric acid, and 9.9 parts of 7% sodium nitritesolution. The resulting solution'o'f the diazo' compound from2-amino-5-sulfobenzoic acid is then added slowly with stirring to acooled solution prepared from 2.6 parts of l-phenyl-3-acetylamino-5-acetoxypyrazole, parts of water, 4 parts of 20% sodium hydroxide, and20 parts of 10% soda ashsolution. Afterthe addition of'thedia'zocompound is complete the reaction mixture is diluted somewhat,neutralized with hydrochloric acid, and treated with salt to precipitatethe yellow azo dye.

This new azo dye dyes wool as an acid dyestufi a yellow tint which isconverted to a reddish yellow by the topchrome process. A similarreddish-yellow shade is obtained if the dyeing is made by the metachromeprocedure.

Example 7 N=N-oH-o-Nm HOaS- OOOH 0:0 N

A solution of 5.9 parts of 2-amino-5-sulfobenzoic acid in 25 parts ofwater and 12 parts of 17% hydrochloric acid is diazotized in the usualmanner with 20.2 parts of '7 sodium nitrite solution. The resultingsolution is then added slowly to a cooled solution of 3.6 parts of1-phenyl-3-aminopyrazolone in 20 parts of water, 8 parts of 20% sodiumhydroxide, and 40 parts of 10% soda ash solution. The product separatesas a thick, gelatinous, reddish-brown solid by acidification withmineral acid, but heating of this slurry to 90 C. results in coagulationto give the desired product in such a form that it is readily removed byfiltration.

The new product dyes Wool as an acid color a yellow shade. When thedyeing is made by the topchrome and metachrome procedures, reddishyellowshades of improved fastness properties are A solution of 2.8 parts of2-amino-4-sulfoloenzoic acid in parts of water and '7 parts of 17%hydrochloric acid is diazotized in the usual manner with 11.5 parts of7% sodium nitrite solution. The resulting solution is then added slowlywith stirring to a cooled solution of 1.8 parts ofl-phenyl-3-aminopyrazolone in 10 parts of Water, 4 parts of 20% sodiumhydroxide, and 20 parts of 10% soda ash solution. After stirring for ashort time, the reaction mixture is diluted and the desired productisolated as a reddish-tan solid by acidification with mineral acid andfiltration.

When applied as an acid dye on wool, a yellow shade is obtained. Theshade is considerably red- 6 dened when-the d y'ei'n-gis *topchrdniddrwflreiithe dyestufi is applied bythe"nietachromemrbceduf;

The diazo compound from 3-amino-4-hydroxy- 5-nitro-benzenesulfonic acidis prepared in the usual manner from 1.8 parts of the amine. Theresulting solution is then added slowly with stirring to a suspension of1.2 parts of l-phenyl-S- amlnopyrazolone in 15 parts of 10% soda ashsolution. As the reaction takes place, a clear solution results and itis necessary to add additional soda ash from time to time to maintain a.weak alkalinity. After the coupling reaction is complete, the productis isolated as a red solid by acidification with mineral acid andfiltration. An additional amount of the dyestuff may be obtained byheating the filtrate to 60 0., adding common salt, and cooling.

This product may be applied on wool as an acid color to give anattractive yellow shade. The shade is considerably redder when thedyestuff is applied by either the topchrome or metachrome procedure.

The metal complexes of the azo dyes of the present invention are notclaimed per se in the present application, as they form the subject ofour copending application Serial No. 567,305 filed Dec. 8, 1944.

In the claims the term an amino group is used generically to cover thegroup NHz and substituted amino groups, such as alkyl, aryl andacylamino groups.

We claim: n

1. Azo dyes represented by the formula in which A is the radical of adiazotized amine selected from the group consisting of amines of thebenzene and naphthalene series having in the ortho position to the aminosubstituent a metallizable substituent selected from in the groupconsisting of hydroxyl, alkoxyl, and carboxylic acid groups, R is anaryl group containing not more than two fused rings, and Y is selectedfrom the group consisting of hydrogen, acyl, and phenyl.

2. Azo dyes according to claim 1 in which the aryl group on thel-nitrogen is a radical of the benzene series.

3. Azo dyes according to claim 1 in which the diazotized amine is anamine of the benzene series.

4. Azo dyes according to claim 1 in which the aryl group on thel-nitrogen is a radical of the benzene series and the diazotized amineis an amine of the benzene series.

5. Azo dyestuffs according to claim 1 in which Y is hydrogen.

6. Azo dyestuffs according to claim 1 in which Y is hydrogen and thearyl group on the l-nitrogen atom is a radical of the benzene series.

7. Azo dyestufis according to claim 1 in which Y is hydrogen and thediazotized amine is an amine of the benzene series.

8. A20 dyestuffs according to claim 1 in which Y is hydrogen, thediazotized amine is an amine of the benzene series and the aryl group onthe l-nitrogen atom is a radical of the benzene series.

ROBERT SIDNEY LONG. CHARLES EDWARD LEWIS.

REFERENCES CITED The following references are of record in the file ofthis patent:

Chem. Abst., vol. 16, page 2863 citing Norral. J. Am. Chem. 800., vol.44, pages 1551-? (1922)

